The present invention relates to composition and a process for treating substrates containing silicon (Si), especially siliceous containing substrate, for rendering them water, oil, stain and dirt repellent.
EP-A-1.171.396 (U.S. Pat. No. 6,379,448) teaches siliceous substrate provided with a fluoro aliphatic silane layer, said layer having excellent mechanical and chemical properties. According to examples, the siliceous substrate is treated with a composition which is prepared before contacting the surface to be treated, by mixing a composition comprising silane and an organic solvent for said silane, and a composition comprising an organic solvent and concentrated hydrochloric acid (HCl). The pot live of the composition when prepared is limited to less than 5 days.
WO 02/30848 teaches a composition for treating a substrate comprising a fluorinated polyether silane, an organic or inorganic acid, water and an organic solvent. Tests have been made by applicant with composition according to said document (composition sold under the trade name ECC-1000). The pot life of the composition is limited whereby the composition has to used in less than 1 day. Furthermore, the layer obtained on a glass substrate with this composition had mechanical properties and chemical resistance properties which were lower than the properties of the layer prepared as taught in EP-A-1.171.396.
U.S. Pat. No. 6,300,379 teaches a method for improving the stability of an aqueous solution comprising a fluoro organo silane, by including in the aqueous composition 1 to 10% by weight based on the total weight of the aqueous solution a surfactant, and 1 to 9% by weight of a glycol ether co-solvent. The amount of fluoro organo silane present in the aqueous composition is comprised between 0.01 and 3%.
The content of said documents is incorporated in the present specification by reference.
Applicant has now discovered that by using a composition containing an organo fluoro silane, an amount of organic solvent sufficient for dissolving the organo fluoro silane and an amount of ammonium or phosphonium compound lower than the amount of organo fluoro silane, it was possible to increase the mechanical properties of the coating and its chemical resistance, even if the organo fluoro silane content of the composition was less than 0.1%. This means that the composition can have a very low content of fluoro silane (while not disturbing the excellent mechanical properties), whereby possible ecological risk can be drastically reduced. Furthermore, it has been observed that compositions substantially water free were still efficient more than 1,2,3 and even 6 months after their preparation, whereby rendering it possible to sell ready to use composition.
The invention relates to a composition suitable for improving the properties of the fluoro silane layer, especially the mechanical properties thereof, in particular to improve the abrasion resistance.
The composition for treating a siliceous containing substrate of the invention comprises:
a first amount of a substantially water insoluble fluoro silane (such as disclosed in EP-A-1.171.396), advantageously fluorinated polyether silane (such as disclosed in WO 02/30848) of the formula:
Rf1xe2x80x94[xe2x80x94Qxe2x80x94SiY3-xR1x]y
wherein Rf1 represent a monovalent or divalent polyfluoropolyether group, Q represents an organic divalent linking group, R1 represents a C1-C4 alkyl group, Y represents a hydrolysable group, x is 0 or 1 and y is 1 or 2;
one or more organic solvents in a quantity sufficient for solubilizing at least substantially completely said first amount of water insoluble polyether silane;
possibly water;
possibly one or more organic or inorganic acid, and
one or more compounds comprising one or more ammonium and/or phosphonium groups, the weight ratio [compounds comprising one or more ammonium and/or phosphonium]/[water insoluble fluoro silane] being advantageously greater than 0.005, preferably greater than 0.01.
The composition of the invention is advantageously free of film forming organic polymer, organic polymer and silane without fluoro atoms. The composition of the invention is advantageously also free of organopolysiloxane. According to a detail, the composition of the invention is free or substantially free of water soluble fluoro silane. The composition of the invention comprises thus preferably as material suitable for making a coating or layer on the substrate, substantially only water insoluble fluoro silane.
The pH of the composition (measured at 25xc2x0 C. by using a LiCl electrode with an open sleeve) is lower than 9, advantageously comprised between 1 and 7.5, preferably comprised between 2 and 7, for example greater than 4 and lower than 7, such as 4, 4.5, 5, 5.5, 6.
According to an embodiment, the amount of ammonium and/or phosphonium compound present in the composition is lower than the first amount, preferably lower than 0.5 time the first amount, most preferably lower than 0.1 time the first amount. It seems that the ammonium and/or phosphonium compound present in the composition acts as a means organizing the reaction of the fluoro organosilane with the face of the siliceous containing substrates, whereby enabling better bonds between the silane layer and the substrate.
The composition of the invention is substantially water free. When the composition is completely water free, the composition is advantageously contacted with the substrate in a humid atmosphere.
The composition of the invention comprises more than 50% by weight organic solvent, advantageously more than 75% by weight, preferably more than 90% by weight, most preferably more than 95% by weight, such as more than 99%, more than 99.5%, or even more than about 99.8%. The composition can be a concentrated composition, for example containing 5% fluoro silane, 1% ammonium/phosphonium compound and 94% organic solvent, said composition being then diluted with organic solvent before its use, so as to apply on the surface to be coated a composition containing advantageously less than 0.5% fluoro silane.
The composition of the invention can comprise one or more carboxylic acids, such as formic acid, citric acid, acetic acid, phthalic acid, tartaric acid, or fluorinated organic acids, such as those disclosed in WO 02/30848. Inorganic acids, such as sulfuric acid, phosphoric acid, hydrochloric acid (HCl), hydrofluoric acid (HF), nitric acid, and mixtures thereof are less preferred. However, the composition can comprise such inorganic acids, especially nitric acid and phosphoric acid. When using acids, the acids or the amount present in the composition will be selected so as to not damage or attack the face to be coated.
The solvent used in the composition of the invention is advantageously selected with the group consisting of aliphatic alcohols, such as methanol, ethanol, isopropylalcohol, ketones, acetone, methyl ethyl ketone, esters, ethers, etc. Suitable organic solvents can be quickly determined by the man skilled in the art by trying to solubilize the water insoluble fluoro silane in the solvent or solvent system he wants to use. Most preferably, the composition comprises at least one halogeno solvent, for example chlorinated solvents, such as chlorinated hydrocarbons, 1,2,2 trichloro-1,1,2-trifluoroethane, fluorinated solvents, such as fluorinated hydrocarbons, hydrofluoroethers, mixtures thereof. Typical examples are perfluorohexane, perflorooctane, pentafluorobutane, CF3CFHFHCF2CF3, methylperfluoroethers, ethyl perfluorobutyl ether, trifluoromethyl-3-ethoxydodxc3xa9cafluorhexane, ethyl nonafluoro isobutylether, methyl nonafluoro butyl ether, and mixtures thereof. Preferred fluoro solvents are trifluoromethyl-3-ethoxydodxc3xa9cafluorhexane, ethyl nonafluoro isobutylether, ethyl nonafluoro butylether, methyl nonafluoro butyl ether, methyl nonafluoro isobutyl ether and mixtures thereof.
Advantageously, the ammonium and/or phosphonium compound is present in the composition at least partly in the form of a salt thereof. For example, the ammonium and/or phosphonium compound present in the composition is present in the form of its chloride salt, its formate salt, its acetate salt, etc. Preferably, the ammonium and/or phosphonium salt is selected so as to be solubilized in the organic solvent used for the fluoro silane.
Ammonium and/or phosphonium compound is advantageously a compound of formula 
In which W is N or P; A1, A2, A3, A4 (which can be similar or different) represent an hydrocarbon group (linear or branched, saturated or unsaturated, substituted or unsubstituted, for example substituted with one or more hydroxyl groups or with one or more halogen atoms) with 1 to 6 carbon atoms, advantageously with less than 3 carbon atoms.
A1, A2, A3, A4 represent preferably each an alkyl group (linear or branched) with 1 to 6 carbon atoms, advantageously with less than 3 carbon atoms, such as with one or two carbon atoms. A1, A2, A3 and A4 represent advantageously a same alkyl group, such as the methyl group.
Specific examples of suitable compounds are tetramethyl ammonium chloride, tetramethyl ammonium bromide, teramethyl ammonium formate, tetramethyl ammonium hydrate, teramethyl ammonium acetate, tetramethyl ammonium sulfate, tetramethyl phosphonium chloride, tetramethyl phosphonium formate, tetra methyl phosphonium citrate, etc. The production and preparation of ammonium and/or phosphonium compounds can be easily found in the literature. Reference can done to U.S. Pat. No. 4,275,235, U.S Pat. No. 4,110,358, WO 91 05003, WO 91 04668, and the prior art cited in said documents.
The composition of the invention can comprise some amino silane, such as amino alkyl silane or amino propyl alkoxy silane, in particular some amino silane used for the preparation of the fluoro silane or the fluorinated polyether silane. The amino silane present in the composition is for example greater than 0.5% the weight of the fluoro silane present in the composition. The weight ratio amino silane/fluoro silane is advantageously greater than 0.01, preferably greater than 0.02, such as 0.05, 0.1, 0.2 or even more (0.3, 0.5, etc.). The reaction of formation of the fluoro silane is for example controlled so as to obtain an end fluoro silane containing the required amount of amino silane. Amino silane can also be added as such at the end of the reaction so as to control the amount of amino silane present.
The composition of the invention comprises according to specific embodiments water, such as from 0.1% up to 10% by weight, such as between 0.1 and 5%, advantageously less than 3%, preferably less than 2%. According to embodiments, the water content of the composition is lower than the fluoro silane content of the composition, for example lower than the ammonium/phosphonium content of the composition.
The invention relates also to a stable and ready-to-use composition, said liquid composition comprising:
less than 0.5% by weight of a substantially water insoluble fluoro silane, advantageously fluorinated polyether silane of the formula:
Rf1xe2x80x94[xe2x80x94Qxe2x80x94SiY3-xR1x]y
wherein Rf1 represent a monovalent or divalent polyfluoropolyether group, Q represents an organic divalent linking group, R1 represents a C1-C4 alkyl group, Y represents a hydrolysable group, x is 0 or 1 and y is 1 or 2;
more than 50% by weight of one or more organic solvents;
possibly water (preferably free of water);
possibly one or more organic or inorganic acid, and
less than 0.5% by weight of one or more compounds comprising ammonium and/or phosphonium.
According to an embodiment, the composition comprises no acid as such, but ammonium and/or phosphonium salts, such as chloride, bromide, formate, acetate, citrate, etc.
The ready-to-use composition of the invention has advantageously one or more characteristics of the composition of the invention.
The invention relates also to a process for coating a face of a silicon (Si) or siliceous containing substrate with a silicon containing layer, in which the face is treated with a composition comprising:
a first amount of a substantially water insoluble fluoro silane, advantageously fluorinated polyether silane of the formula:
Rf1xe2x80x94[xe2x80x94Qxe2x80x94SiY3-xR1x]y
wherein Rf1 represent a monovalent or divalent polyfluoropolyether group, Q represents an organic divalent linking group, R1 represents a C1-C4 alkyl group, Y represents a hydrolysable group, x is 0 or 1 and y is 1 or 2;
one or more organic solvents in a quantity sufficient for solubilizing at least substantially completely said first amount of water insoluble polyether silane;
possibly water;
possibly one or more organic or inorganic acid, and
one or more compounds comprising ammonium and/or phosphonium.
The composition used in the process is advantageously a composition of the invention, for example a ready-to-use composition of the invention.
The composition can be applied on various ways on the substrate, such as by contacting the substrate with the liquid composition, by dipping, brushing, spraying, wiping, atomising, flowing, falling, etc.
Advantageously, prior to be contacted with the solution, the said part of the face is washed, for example degreased, while after to be contacted with the solution, the said part of the face is rinsed, for example with a solvent, a polar solvent, especially with the solvent used in the fluoro silane composition. Prior contacting the substrate with the composition of the invention, it is advantageous to treat the surface with a biocide and/or with an ammonium and/or phosphonium compound. When pretreating the substrate, the face of the substrate to be treated is advantageously dried or the possible liquid water present on the face is removed by mechanical action, by adsorption or by physical actions.
According to an embodiment of the process, the drying or curing of the composition is carried out at room temperature. A substantially complete drying or curing of the fluoro silane layer can be reached after about 24 hours.
Preferably, possibly after drying or removal of solvent or water, the said face is subjected to a heat treatment at a temperature from 30xc2x0 C. up to about 250xc2x0 C., for example from 40xc2x0 C. to about 200xc2x0 C., in an oxidative atmosphere or up to about 350xc2x0 C. in a non-oxidative atmosphere.
During the contact of the substrate with the composition as well as during the curing step, the atmosphere is controlled. For example, the humidity level of the gas present in the room where the substrate is contacted with the composition. The temperature is also kept advantageously as low as possible, for example at a temperature comprised between 5 and 65xc2x0 C., such as a temperature comprised between 20 and 50xc2x0 C. The treatment can be made under pressure.
The siliceous substrate is advantageously selected from the group consisting of glass, glass containing substrates, ceramics and silicate surfaces. Other possible substrates are listed in WO 02/30848, the content of which is incorporated by reference.
Advantageously, the amount of ammonium and/or phosphonium compound present in the composition is lower than the first amount, preferably lower than 0.5 time the first amount, most preferably lower than 0.1 time the first amount. For example, the weight ratio (ammonium compound or phosphonium compound or ammonium+phosphonium compound or mixture thereof)/fluoro silane is 0.05; 0.03; 0.02; 0.01 or even less.
The composition applied on the substrate is substantially water free.
According to a specific embodiment of a process of the invention, the face of the substrate to be treated is first treated with a first composition comprising:
a first amount of a substantially water insoluble fluoro silane, advantageously a water insoluble fluorinated polyether silane of the formula:
Rf1xe2x80x94[xe2x80x94Qxe2x80x94SiY3-xR1x]y
wherein Rf1 represent a monovalent or divalent polyfluoropolyether group, Q represents an organic divalent linking group, R1 represents a C1-C4 alkyl group, Y represents a hydrolysable group, x is 0 or 1 and y is 1 or 2;
one or more organic solvents in a quantity sufficient for solubilizing at least substantially completely said first amount of water insoluble polyether silane;
possibly water; and
possibly one or more organic or inorganic acid, and thereafter with a second composition comprising:
one ammonium and/or phosphonium compound selected from the group consisting of compounds with at least one ammonium group, compounds with at least one phosphonium group, compounds with at least one ammonium group and with at least one phosphonium group, and mixtures thereof, the quantity of said composition being advantageously such that the weight ratio ammonium and/or phosphonium compound of the second composition applied on the substrate/water insoluble fluoro silane present in the first solution applied on the substrate is greater than 0.005.
Advantageously, prior to be contacted with the solution, the said part of the face is washed, for example degreased, while after to be contacted with the solution, the said part of the face is rinsed, for example with a solvent for the fluoro silane compound.
The drying and curing of the composition applied onto the substrate is preferably carried out after removal of the excess of composition present on the substrate, for example by using a wool cloth or fabric, a cotton cloth or fabric, etc. The said cloth or fabric can also be used for ensuring a good application of the composition on the whole surface, especially along the edge of the siliceous substrate. The removal of excess of composition present on the surface can also be removed by applying on said surface water or solvent, such as a large amount of water.
The application, as well as the drying and curing of the composition can be carried at outside temperature in an uncleaned (non-cleaned) atmosphere. For example the application, as well as the drying and curing can be carried out at temperature fromxe2x88x9250xc2x0 C. up to the degradation of the fluoro silane layer. It is obvious that the application and the drying and curing of the composition can be carried out in a cleaned atmosphere. It is for example possible to apply the composition on the glass sheet or glass pieces just after its manufacture, for example after a cooling step.
When the drying is carried out at a lower temperature, the time required for obtaining a sufficient drying and curing will be longer.
The application is for example carried out at a temperature comprised between 0 and 50xc2x0 C. The drying and curing can also be carried out in this range of temperature.
According to an embodiment of the process, the drying or curing of the composition is carried out at room temperature, without requiring a cleaned atmosphere. A substantially complete drying or curing of the fluoro silane layer can be reached after about 24 hours.
Preferably, possibly after drying or removal of solvent or water, the said face is subjected to a heat treatment at a temperature from 30xc2x0 C. up to about 250xc2x0 C., for example from 40xc2x0 C. to about 200xc2x0 C., in an oxidative atmosphere or up to about 350xc2x0 C. in a non-oxidative atmosphere.
The said composition is advantageously at least substantially free of organic polymer, of film forming organic polymer, of silane without fluorine atoms, so that the layer is substantially only formed by fluoro silane.
The drying step can be a mechanical removal of excess of composition and polar solvent present on the siliceous substrate or of an excess of water or solvent (preferably polar solvent) used for rinsing the substrate after being contacted with the composition. However, advantageously, prior to be contacted with the solution, the said part of the face is washed (for example degreased), while after to be contacted with the solution, the said part of the face is rinsed. The drying step is preferably carried out at least partly at a temperature sufficient for making covalent bonds (oxygen bonds) between the layer and the substrate. Said drying can be carried out at a temperature comprised between xe2x88x9220xc2x0 C. and 250xc2x0 C. in an oxidative atmosphere and between xe2x88x9220xc2x0 C. and about 350xc2x0 C. in a non-oxidative atmosphere. The drying can be done possibly under vacuum.
Before contacting a face of the siliceous substrate with the silane composition, the said face can be partly or completely treated so as to ensure that the surface is dust free, fat free and free of silicone or other compounds grafted to the face of the siliceous substrate on which a fluoro silane layer according to the invention has to be applied, and/or so as to ensure a kind of abrasion of the said face (for example by projection of small high resistant particles or particle dusts, for example of SiC particles or dust).
Such washing or cleaning pretreatment includes ultrasonic cleaning; washing with an aqueous mixture of organic solvent, e.g., a 50:50 mixture of isopropanol:water or ethanol:water; activated gas treatment, e.g., treatment with low temperature plasma or corona discharge, and chemical treatment such as hydroxylation, i.e., etching of the surface with an aqueous solution of alkali, e.g., sodium hydroxide or potassium hydroxide, that may also contain a fluorosurfactant, washing the glass with an aqueous solution that may contain a low foaming, easily rinsed detergent, followed by rinsing and drying with a lint-free cloth; and ultrasonic bath treatment in heated (about 50.degree. C.) wash (preferably deionized) water, followed by rinsing and drying. A pre-cleaning with an alcohol-based cleaner or organic solvent prior to washing may be required to remove adhesives from labels or tapes. Cleaning may also advantageously comprise a polishing step. After drying, the base or glass sheet may be washed with a polar solvent, specifically a chlorinated solvent and/or a fluorinated solvent. Alternatively, and preferably, the base is exposed to an oxidizing atmosphere to improve the reactivation of the glass; for example, to a combination of ozone and UV radiation. It is clear that the siliceous substrate or glass can be submitted to various washing and cleaning pre-treatments.
For removing silicone oil or compounds possibly grafted to the siliceous substrate, the substrate can be treated with ammonium fluoride solution, potassium hydroxide (at boiling temperature), HF, Silstrip Liquid(copyright) of PENN-WHITE (UK), etc.
In the process according to the invention, the composition when being applied on the substrate still contains silane oligomer (product of the condensation of silane monomer or silanol) with up to 6 Si atoms, preferably with up to 3 Si atoms.
Polar solvents (water is not a solvent for the fluoro silane used in the process of the invention) which can be used in the process of the invention are for example halogeno solvents, fluorine-containing polar solvents, aliphatic or aromatic polar solvents, ketones, esters and mixtures thereof, such as alcohol, ethyl acetate, tetrahydrofuran, mono ethylene glycol, diethylene glycol, triethylene glycol, etc. Advantageously, the polar solvent is selected from the group consisting of C1-C6 alkanol, and aliphatic alcohols of the empirical formula:
[(R3)iR4](C1-C6)OH
wherein R3 and R4 are each C1-C4 alkoxy, and i is the integer 0 or 1, and mixtures thereof. Advantageously, the organic polar solvent has at least one OH group, but preferably only one OH group. Preferred examples of polar solvents are methanol, ethanol, 2-ethoxyethanol, 2-(2-methoxyethoxy) ethanol, 2-methoxy ethanol, 2-(2-ethoxymethoxy) ethanol, 1-propanol, 2-propanol, 1-methoxy-2-propanol, and mixtures thereof (methanol, ethanol, methoxy-ethanol, propanol and mixtures thereof being the most preferred).
Possible halogeno solvents are chlorinated solvents, such as chlorinated hydrocarbons, 1,2,2 trichloro-1,1,2-trifluoroethane, fluorinated solvents, such as fluorinated hydrocarbons, hydrofluoroethers, mixtures thereof. Typical examples are perfluorohexane, perflorooctane, pentafluorobutane, CF3CFHFHCF2CF3, methylperfluoroethers, ethyl perfluorobutyl ether, trifluoromethyl-3-ethoxydodxc3xa9cafluorhexane, ethyl nonafluoro isobutylether, methyl nonafluoro butyl ether, and mixtures thereof. Preferred fluoro solvents are trifluoromethyl-3-ethoxydodxc3xa9cafluorhexane, ethyl nonafluoro isobutylether, methyl nonafluoro butyl ether, and mixtures thereof.
The siliceous containing substrate is preferably contacted with the solution at a temperature comprised between 0 and 50xc2x0 C., for example at room temperature or at a temperature lower than 15xc2x0 C. The application can be carried out in a non cleaned atmosphere. Low temperatures are preferred so as to avoid as much as possible cross-linking of silane and so as to reduce as much as possible the formation of larger oligomer in the composition before being applied on the substrate.
In an advantageous embodiment of the process according to the invention, after applying the composition onto a face of the substrate, the said face is submitted to a rubbing with a cloth or fabric, especially with a wool fabric or cloth. It seems that the rubbing of material, such as a wool fabric, suitable for creating static force against the surface of the substrate on which the composition has been applied is advantageous for ensuring an excellent application of the composition onto the said face. The said rubbing can be done manually or mechanically, for example by means of a rotating head provided with a wool fabric.
In an advantageous embodiment of the process, after contacting the said face of the substrate with the composition, the said face is rinsed (for example, by means of water, a polar solvent or a mixture thereof) so as to remove the excess of fluoro silane present on the substrate and dried at least partly at a temperature lower than 50xc2x0 C. (for example by means of dry air, air having a relative humidity lower than 60%). Preferably, the drying is carried out in a first step by a mechanical treatment so as to remove at most completely the solvent present on the surface of the substrate.
After a possible drying step of the substrate and/or the mechanical removal of the excess of fluoro silane, it is advantageous to submit the face of the substrate to a heat treatment at a temperature above 30xc2x0 C., for example from 40xc2x0 C. up to 200xc2x0 C., so as to increase the formation of bonds (oxygen bonds) of fluoro silane oligomers with the substrate and therebetween. The said heat treatment can be carried out at higher temperature lower than the degradation temperature of the fluoro silane, for example up to 350xc2x0 C., in a non oxidative atmosphere. In oxidative atmosphere, it is advisable to use about 250xc2x0 C. as maximum temperature. Such a heat treatment is also a drying step.
The drying step can also be carried out at low temperature, for example at room temperature in a cleaned atmosphere as well as in a non-cleaned atmosphere. In this case, the time necessary for obtaining a sufficient condensation of fluoro silane with the substrate is longer (for example 15 to 36 hours, especially about 24 hours).
The process of the invention can be carried out on various siliceous containing substrates, such as glass, ceramics, ceramics tiles and silicate surfaces.
Examples of possible substrate are:
a glass sheet, glass sheet for a window, a car window, boat window, window of airplanes, control windows of reactors, etc.; the cleaning of the glass sheet being very easy, there are less impacts of insects, less dirt, . . . , especially a wiper blade provided with a fluoro layer or a fluorinated layer (for example a wiper blade according to WO 9812085) is used with such windows;
glasses, wineglasses, etc.; whereby a correct washing of the glasses can be carried by using only water; contact lenses, objectives (for example of microscopes, cameras, etc.);
a solgel containing SiO2 particles;
SiO2 particles used in toner, as additives in organic or inorganic composition, in cement, in paints, in fluidised bed, in filters (as filter cake for example), in screenings, in classifications processes, in heavy media separation processes, etc.;
Lamps, neon lamps, etc.;
Transparent protection sheet of solar electrical cells;
Bottles, vials, tubes, glass syringes, etc., said bottles, vials, tubes, syringes having at least the inner face provided with a fluoro layer and preferably also the outer face provided with a fluoro layer, so that the washing and/or the sterilisation and/or removal of labels, glued labels is easier, the said bottles, vials and tubes being advantageously closed by means of a stopper (for example a rubber stopper) provided with a fluoro layer or a fluorinated layer so as to have a good sealing contact between the stopper and the neck of the bottles, vials or tubes, while the said syringes have advantageously a plunger provided with a fluoro layer or a fluorinated layer so as to have a good sealing and a low friction when moving the plunger;
Glass fibres, such as optical fibres, glass wool for isolation purposes, for filtering purposes, etc;
High voltage isolators;
Kiezelghur particles for example for filtering purposes;
Analysis tube, control tube, level control system;
Reactor, chemical reactor, condensers, falling film exchangers, reactors, absorbers, etc.;
Sanitary installations;
Enamel or porcelain surfaces, such as wash basin or vat, etc.;
Siliceous substrate with an anti adhesion surface for the manufacture of micro lenses, etc.;
Siliceous substrates as casting moulds;
Siliceous packing elements for towers, such as absorption tower;
Earthenware;
Glass films;
Wood,
Silicon containing steel;
Composite materials;
paper containing SiO2;
etc.
The composition of the invention, especially the ready-to-use composition of the invention can be prepared from a kit comprising at least two distinct compartments or chambers, a first comprising one or more solvents, one ammonium and/or phosphonium compound (such as in the form of one of its salts), possibly water and possibly one or more organic or inorganic acids; and the second compartment or chamber comprising the fluoro silane and one or more solvent (especially at least one solvent being a halogeno or halogenated solvent, such as a fluorinated solvent)